摘要:
The reaction of [1,3-{Pd[2,3,4-(MeO)(3)C6HC(H)=NCH2](mu-O2CMe)}(2)C6H4] (1), with triphenylphosphine in a 1:2 molar ratio gave the doubly cyclometallated complex [1,3-{Pd[2,3,4-(MeO)(3)C6HC(H)=NCH2](OAc)(PPh3)}(2)C6H4] (3), after cleavage of the two acetate-bridges. Treatment of the chloro-bridged complexes [1,3-{Pd[2,3,4-(MeO)(3)C6HC(H)=NCH2](mu-Cl)}(2)C6H4](2) (2) and [1,4-{Pd[2,3,4-(MeO)(3)C6HC(H)=N-CH2](mu-Cl)}(2)C6H4](2) (8) with the tertiary monophosphines PPh3, P(p-MeOC6H4)(3) and P(p-NMe2C6H4)Ph-2 gave the doubly cyclometallated complexes [1,3-{Pd[2,3,4-(MeO)(3)C6HC(H)=NCH2](Cl)(PR3)}(2)C6H4] (PR3=PPh3, 4; P(p-MeOC6H4)(3), 5; P(p-NMe2C6H4)Ph-2, 6) and [1,4-{Pd[2,3,4-(MeO)(3)C6HC(H)=NCH2](Cl)(PR3))(2)C6H4] (PR3 = PPh3, 9; P(p-MeOC6H4)(3), 10; P(p-NMe2C6H4)Ph-2, 11). Reaction of complex 4 with PPh3 did not yield the expected non-cyclometallated complex. Reaction of complexes 2 and 8 with the tertiary diphosphine cis-Ph2PCH CHPPh2, in a 1:4 molar ratio and NaClO4, yielded the doubly cyclometallated complexes [1,3-{Pd[2,3,4-(MeO)(3)C6HC(H)-NCH2](Ph2PCH=CHPPh2-P,P)}(2)C6H4][ClO4](2) (7) and [1,4-{Pd[2,3,4-(MeO)(3)C6HC(H)=NCH2](Ph2PCH=CHPPh2-P,P)}(2)C6H4][ClO4](2) (12), respectively, with the diphosphine as a chelating bidentate ligand. (C) 2002 Elsevier Science Ltd. All rights reserved.